Derivatives of 4-((aryloxy)phenoxy)alkenols and their herbicidal uses

ABSTRACT

Derivatives of 4-((aryloxy)phenoxy)alkenols, their preparation and use as active herbicides for the postemergent control of grassy weeds and especially the control of said weeds in the presence of corn plants are disclosed.

This is a divisional of application Ser. No. 07/367,274, filed Jun. 16,1989, now U.S. Pat. No. 5,034,050, which in turn is a continuation ofapplication Ser. No. 150,803, filed Feb. 1, 1988, now abandoned, whichin turn is a continuation of application Ser. No. 837,229, filed Mar. 7,1986, now U.S. Pat. No. 4,731,108.

BACKGROUND OF THE INVENTION

Highly active herbicidal compounds of the class constitutingaryloxyphenoxyalkanoic, and aryloxyphenoxyalkenoic acids and relatedcompounds have been described in the patent literature. These compoundshave been prepared by making derivatives of the acid function thereofand bearing various groups or substituents on, primarily, the arylstructure. Such compounds in which the aryloxy and O-alkanoic acidfunctions respectively are disposed in 1,4 relation on the phenyl group,are especially active against grassy, i.e., gramineous weeds whiledisplaying little or no herbicidal activity against broadleaf plantsand, often, slight activity against cereal grains. However, thesecompounds as a group are generally injurious to corn, i.e., maize, andare of little use for controlling grassy weeds in corn crops.

FIELD OF THE INVENTION

The present invention relates to novel highly active herbicidalcompounds, compositions containing said compound and methods for thepostemergent use thereof in the control of grassy weeds, especially inthe presence of grass crops such as corn. The invention relatesespecially to novel derivatives of 4-((aryloxy)phenoxy)alkenolcompositions containing said compounds and the postemergent herbicidaluse thereof.

SUMMARY OF THE INVENTION

It has now been discovered that esters of aryloxyphenoxyalkenols,particularly the pentenols, are highly active herbicidal compoundseffective in the postemergent, systemic kill or control of grassy weedswhile exhibiting little herbicidal action against corn.

The active derivatives of aryloxyphenoxyalkenols of the presentinvention correspond to the formula ##STR1## wherein Ar represents##STR2## Y and Y¹ each independently represent --H or --F; X represents--H, --Br or --Cl;

R represents methyl or ethyl;

T represents ##STR3## and the cis (Z) or trans (E) stereoisomers thereofor ##STR4## A represents .tbd.N or .tbd.CH; G represents in the 5 or 6ring position, --Br, --Cl, --F or --CF₃ ;

a represents the integer 0, 1 or 2;

b represents the integer 1 or 2;

P represents --Br, --Cl, --I or --CF₃ ;

Q represents --Br, --Cl, --F or --CF₃ ;

R¹ represents --OSO₂ R², ##STR5## R² represents C₁ -C₄ alkyl, C₂ -C₄alkenyl or --NR⁴ R⁵ ;

R³ represents C₂ -C₄ alkenyl, C₁ -C₄ alkyl, --NR⁴ R⁵ or ##STR6## whereinR⁴ and R⁵ each independently represent --H or C₁ -C₄ alkyl;

D represents C₁ -C₄ -alkyl, --Br, --Cl, --NO₂, --CF₃, --OCF₃, ##STR7##wherein R⁶ represents C₁ -C₄ alkyl and m represents an integer of from0-3, inclusive.

The present invention also encompasses compositions containing one ormore of these active compounds as well as methods of using suchcompounds or compositions in the control of grassy weeds, particularlyin the presence of corn.

The active compounds of the present invention, hereinafter referred toas "active compounds" or "active ingredients", have been found to beuseful as herbicides for the postemergent kill and control ofundesirable vegetation, for example, grassy or graminaceous weeds in thepresence of corn plants.

The term "herbicide" is used herein to mean an active ingredient whichcontrols or adversely modifies the growth of plants because ofphytotoxic or other effects substantial enough to seriously retard thegrowth of the plant or further to damage the plant sufficiently to killthe plant.

The terms "growth controlling" or "herbicidally effective" amount areemployed to designate an amount of active ingredient which causes amodifying effect and includes deviations from natural development,killing, regulation, dessication, retardation, and the like.

The term "plants" means established vegetation.

The terms "control" or "controlling" as it relates to plant growth hasthe same meaning as employed hereinabove for the term "herbicide".

The term "C₁ -C₄ alkyl" as employed in the present specification andclaims designates alkyl groups which can be straight or branched chaincontaining from 1 to 4 carbon atoms or cycloalkyl of 3 or 4 carbonatoms.

In the present invention, it is to be noted that all substituent groupsare sterically compatible with each other. The term "stericallycompatible" is employed to designate substituent groups which are notaffected by steric hindrance as defined in "The Condensed ChemicalDictionary", 7th edition, Reinhold Publishing Co., N.Y., page 893 (1966)which definition is as follows:

"steric hindrance. A characteristic of molecular structure in which themolecules have a spatial arrangement of their atoms such that a givenreaction with another molecule is prevented or retarded in rate."

Steric hindrance may be further defined as compounds having substituentswhose physical bulk does not require confinement within volumesinsufficient for the exercise of their normal behavior as discussed in"Organic Chemistry" of D. J. Cram and G. Hammon, 2nd edition,McGraw-Hill Book Company, N.Y., page 215 (1964).

The active compounds of the present invention contain the opticallyactive center ##STR8## and can exist in optically active stereoisomericforms such as the R and S enantiomeric forms. The use of the variousmixtures and racemates of the above isomers are within the scope of thepresent invention. Additionally, the R enantiomer of such compounds havebeen found to be more active biologically than the S enantiomer and maybe used whenever the greater activity justifies the extra expenses forthe use of this isomer.

A general discussion of the isomer activity difference phenomenon can befound in A. Albert, Selective Toxicity, 4th edition, Met Luen & Co.,Ltd., London, 1968, pp. 387-390 and more particular discussions in A.Fredga and B. Aberg, "Stereoisomerism in plant growth regulators of theauxin type", Ann. Rev. Plant Physiology 16:53-72, 1965, and in E. J.Lien, J. F. R. DeMiranda and E. J. Airens, "Quantitativestructure-activity correlation of optical isomers", MolecularPharmacology 12:598-604, 1976.

The active compounds or ingredients of the present invention aregenerally oils or low melting crystalline solids at ambient temperatureswhich are soluble in many organic solvents commonly employed asherbicidal carriers.

Representative active compounds of the present invention are set forthbelow in Tables 1, 2, 3, 4 and 5.

                                      TABLE 1                                     __________________________________________________________________________     ##STR9##                                                                     P   X  Y  Y.sup.1                                                                          R    T             R.sup.1                                       __________________________________________________________________________    Br  Cl H  H  CH.sub.3                                                                           CHCH          OC(O)CH.sub.3                                 Cl  Cl H  H  CH.sub.3                                                                           CHCH          OC(O)- -n-C.sub.4 H.sub.9                     CF.sub.3                                                                          Cl H  H  CH.sub.3                                                                           CHCH          OSO.sub.2 CH(CH.sub.3).sub.2                  Br  Cl H  H  C.sub.2 H.sub.5                                                                    (CH.sub.2 CH .sub.2) .sub.2(CHCH) .sub.2                                                    OC(S)CH.sub.3                                 l   Br F  F  C.sub.2 H.sub.5                                                                     (CHCH) .sub.2                                                                              OC(O)C.sub.2 H.sub.5                          CF.sub.3                                                                          Br F  H  CH.sub.3                                                                           CHCH          OC(O)CH.sub.3                                 l   Cl F  F  CH.sub.3                                                                           (CHCH) .sub.2 OSO.sub.2 CH.sub.3                            CF.sub.3                                                                          Cl H  H  CH.sub.3                                                                           CHCH          OSO.sub.2 CH.sub.3                            CF.sub.3                                                                          Cl H  H  C.sub.2 H.sub.5                                                                    CHCH          OC(S)CH.sub.3                                 Cl  Cl H  H  CH.sub.3                                                                           CHCH          OC(O)N(CH.sub.3).sub.2                        CF.sub.3                                                                          Cl F  F  CH.sub.3                                                                           CHCH          OC(O)NHCH.sub.3                               CF.sub.3                                                                          Br H  H  CH.sub.3                                                                           CHCH          OC(O)NH- -n-C.sub.4 H.sub.9                   Cl  Cl H  H  CH.sub.3                                                                           (CHCH) .sub.2 OSO.sub.2 NHC.sub.2 H.sub.5                    CF.sub.3                                                                         Cl H  H  CH.sub.3                                                                           CHCH          OSO.sub.2 CH(CH.sub.3).sub.2                  l   Br H  H  C.sub.2 H.sub.5                                                                    CH.sub.2 CH.sub.2 CHCH                                                                      OSO.sub.2 C.sub.3 H.sub.7                     Cl  Cl H  H  CH.sub.3                                                                           CHCH          OC(S)N(CH.sub.3).sub.2                        CF.sub.3                                                                          Br H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR10##                                    Br  Br H  H  CH.sub.3                                                                           CHCH          OC(O)CHCH.sub.2                               l   Br F  H  CH.sub.3                                                                           CHCH          OC(O)N(CH.sub.3)C.sub.2 H.sub.5               CF.sub.3                                                                          Cl H  H  CH.sub.3                                                                           CHCH          OSO.sub.2 NHCH(CH.sub.3).sub.2                Cl  Cl H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR11##                                    Cl  Cl H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR12##                                    Br  Br H  H  CH.sub.3                                                                           CHCH          OC(O)NHC.sub.2 H.sub.5                        CF.sub.3                                                                          Cl H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR13##                                    __________________________________________________________________________

                  TABLE 2                                                         ______________________________________                                         ##STR14##                                                                    P     Y      Y.sup.1                                                                              R     T         R.sup.1                                   ______________________________________                                        CF.sub.3                                                                            H      H      CH.sub.3                                                                            CHCH      OC(O)CH.sub.3                             l     F      F      CH.sub.3                                                                            CHCH      OC(O)NHCH.sub.3                           CF.sub.3                                                                            H      H      CH.sub.3                                                                            CC        OC(O)CH.sub.3                             l     H      H      CH.sub.3                                                                            CHCH      OSO.sub.2 C(CH.sub.3).sub.2               Br    H      H      CH.sub.3                                                                            (CHCH) .sub.2                                                                           OSO.sub.2 C(CH.sub.3).sub.2               ______________________________________                                    

                                      TABLE 3                                     __________________________________________________________________________     ##STR15##                                                                    A     Q   Y  Y.sup.1                                                                          R    T             R.sup.1                                    __________________________________________________________________________    CH    F   H  H  C.sub.2 H.sub.5                                                                    (CHCH) .sub.2 OC(O)C.sub.2 H.sub.5                       N     Cl  H  H  CH.sub.3                                                                           CHCH          OC(O)CH.sub.3                              N     Cl  H  H  CH   CHCH          OC(O)NHCH.sub.3                            N     Cl  H  H  CH.sub.3                                                                           CH CH                                                                                        ##STR16##                                 CH    Br  H  H  CH.sub.3                                                                           CHCH          OC(O)CH(CH.sub.3).sub.2                    N     Cl  H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR17##                                 N     Cl  H  H  CH.sub.3                                                                           CHCH          OSO.sub.2 CH(CH.sub.3).sub.2               N     Cl  H  H  CH.sub.3                                                                           CHCH          OSO.sub.2 NHCH(CH.sub.3).sub.2             N     Cl  H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR18##                                 N     Cl  H  H  CH.sub.3                                                                           CHCH          OC(O)C(CH.sub.3).sub.3                     N     Cl  H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR19##                                 CH    CF.sub.3                                                                          H  H  C.sub.2 H.sub.5                                                                    (CHCH) .sub.2 OC(O)N(CH.sub.3).sub.2                     N     Cl  H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR20##                                 N     Cl  H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR21##                                 N     Cl  H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR22##                                 N     Cl  H  H  CH.sub.3                                                                           CHCH          OSO.sub.2 CH.sub.3                         CH    Cl  F  F  C.sub.2 H.sub.5                                                                    (CH.sub.2 CH .sub.2) .sub.2(CHCH) .sub.2                                                    OC(S)CH.sub.3                              N     Cl  H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR23##                                 N     Cl  H  H  CH.sub.3                                                                           CHCH          OC(O)C.sub.3 H.sub.7                       N     Cl  H  H  CH.sub.3                                                                           CHCH          OSO.sub.2 - -n-C.sub.4 H.sub.9              N    Cl  H  H  CH.sub.3                                                                           CHCH          OSO.sub.2 C.sub.3 H.sub.7                  N     Cl  H  H  CH.sub.3                                                                           CHCH          OSO.sub.2 C.sub.2 H.sub.5                  CH    Cl  H  H  CH.sub.3                                                                           CHCH          OSO.sub.2 CH(CH.sub.3).sub.2               N     Cl  H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR24##                                 CH    Cl  H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR25##                                 CH    Cl  H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR26##                                 N     Cl  H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR27##                                 N     Cl  H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR28##                                 N     Cl  H  H  CH.sub.3                                                                           CHCH                                                                                         ##STR29##                                 __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________     ##STR30##                                                                    G   L  Y  Y.sup.1                                                                          R   T            R.sup.1                                         __________________________________________________________________________    6-CF.sub.3                                                                        S  F  F  CH.sub.3                                                                          CHCH         OC(O)C.sub.2 H.sub.5                            6-Cl                                                                              S  H  H  CH.sub.3                                                                          CHCH         OC(O)CH.sub.3                                   6-Br                                                                              S  F  H  CH.sub.3                                                                          CHCH         OC(O)CH.sub.3                                   6-F S  H  H  CH.sub.3                                                                          CHCH         OC(O)CH.sub.3                                   6-Cl                                                                              O  H  H  CH.sub.3                                                                          CH.sub.2 CH.sub.2 CHCH                                                                     OC(O)CH.sub.3                                   5-Cl                                                                              O  H  F  CH.sub.3                                                                          CHCH         OC(O)CH.sub.3                                   __________________________________________________________________________

                                      TABLE 5                                     __________________________________________________________________________     ##STR31##                                                                    G   Y   Y.sup.1                                                                           R    T         R.sup.1                                            __________________________________________________________________________    6-CF.sub.3                                                                        H   H   C.sub.2 H.sub.5                                                                    (CHCH) .sub.2                                                                           OC(O)- -n-C.sub.4 H.sub.9                          -6-Cl                                                                             H   H   CH.sub.3                                                                           CHCH                                                                                     ##STR32##                                         -5-CF.sub.3                                                                       F   F   CH.sub.3                                                                           CHCH      OC(O)CH.sub.3                                      6-Cl                                                                              H   H   CH.sub.3                                                                           CHCH      OC(O)CH.sub.3                                      6-Cl                                                                              H   H   CH.sub.3                                                                           CHCH      OSO.sub.2 CH(CH.sub.3).sub.2                       __________________________________________________________________________

The preferred compounds of the present invention include those compoundsof Formula I wherein Ar is as follows:

5-chloro-2-pyridyl

5-trifluoromethyl-2-pyridyl

3,5-dichloro-2-pyridyl

5-chloro-5-trifluoromethyl-2-pyridyl

5-chloro-3-fluoro-2-pyridyl

6-chloro-2-quinolinyl

6fluoro-2-quinolinyl

6-chloro-2-quinoxalinyl

6-fluoro-2-quinoxalinyl

6-chloro-2-benzothiazolyl

5-chloro-2-benzoxazolyl

5 -chloro-2-thiazolopyridyl

5-fluoro-2-thiazolopyridyl.

These above compounds are even more preferred when R is methyl, Y and Y¹are hydrogen, a is 0 and b is 1.

The active ingredients of Formula I wherein R¹ is --OSO₂ R² constitute apreferred embodiment and active ingredients wherein R¹ is --O--C(O)R³constitute a further preferred embodiment.

The active ingredients of the above Formula I can be prepared inaccordance with one or more of the following procedures.

The compounds of the present invention wherein R¹ is ##STR33## or --OSO₂R² where R² and R³ are other than --NHR⁵ and R⁴ is other than hydrogencan be prepared by the condensation of an appropriate4-((aryloxy)phenoxy)alkenol corresponding to the formula ##STR34## withan appropriate halide corresponding to the formula

    Hal-R.sup.7                                                (III)

wherein R⁷ is ##STR35## or --SO₂ R² and R² and R⁴ are as further defineddirectly hereinabove in the presence of an inert solvent and a hydrogenhalide absorber (acid scavenger) to obtain the desired compoundcorresponding to the formula ##STR36## wherein in Formulae Ia, II andIII; Ar, Y, Y¹, R, R⁷ and T are as hereinabove defined and hal- ischloro or bromo.

The reaction is generally carried out at a temperature in the range offrom about 0° to about 25° C.

While not normally necessary, a catalyst can be employed, if desired.Representative catalysts include, for example, 4-dimethylaminopyridineand 1,4-diazabicyclo-2,2,2-octane.

Representative inert solvents for this reaction include, for example,chlorinated hydrocarbons (for example, methylene chloride), ether,toluene, pyridine, hexane, acetonitrile and the like.

Representative hydrogen halide absorbers include tertiary amines, alkalimetal hydroxides and alkali metal carbonates. Additionally, whenpyridine is employed as the solvent, it can also function as thehydrogen halide absorber.

The compounds of the present invention wherein R¹ is ##STR37## and R³ isother than --NR⁴ R⁵ can be prepared by the reaction of an appropriatealkenol corresponding to Formula II with an ester corresponding to theformula ##STR38## wherein R, L and R³ are as hereinabove defined. Thisreaction can be carried out employing the same solvents and conditionsas set forth hereinabove for the reaction between the reactants ofFormulae II and III.

Additionally, when, R¹ is ##STR39## and R³ is other than --NR⁴ R⁵ anappropriate anhydride corresponding to the formula wherein R³ is ashereinbefore defined can be reacted with the alkenol or thiolcorresponding to Formula II ##STR40## employing the same solvents andconditions as set forth hereinabove for the reaction between thereactants of Formulae II and III.

The specific reaction times employed in the hereinabove and hereinafterset forth preparative procedures vary considerably and are dependentupon factors such as the solvent, base, catalyst, if employed, reactiontemperature and the reactivity of the specific reactants employed. Thereactions are for the most part complete in a period of from about 30minutes to about 12 hours or more.

The above-indicated active compounds of the present invention can beprepared in an alternative procedure by the reaction of substantiallyequimolar amounts of a compound of Formula II with a strong alkali basesuch as sodium hydride or the like to irreversibly abstract the hydrogenproton followed by the direct treatment of the resulting alkali metalalkoxide material without separation, with an acid halide of FormulaIII.

The compounds of the present invention wherein R¹ is ##STR41## and R³ is--NHR⁵ can be prepared by the condensation of an appropriate alkenol ofFormula II with an appropriate isocyanate or isothiocyanatecorresponding to the formula

    R.sup.5 NC═L                                           (V)

wherein L and R⁵ are as hereinbefore defined. The reaction is generallycarried out in the presence of an inert solvent such as methylenechloride or toluene at ambient temperatures, though the use of highertemperatures could be necessary depending on the L═CNR⁵ reactant toeffect condensation. A catalytic amount of a base such as, for example,triethylamine, is sometimes beneficial. The isocyanate andisothiocyanate reactants are all known compounds of commerce.

The compounds of the present invention which correspond to the formula##STR42## wherein Ar, Y, Y¹, R, T and m are as hereinbefore set forthand D¹ is ##STR43## and R⁶ is as hereinbefore defined, can be preparedby the reaction, at ambient temperature, of an appropriate4-((aryloxy)phenoxy)-alkenol corresponding to the formula ##STR44##wherein Ar, Y, Y¹, R and T are as hereinbefore set forth with anappropriate substituted benzoic acid corresponding to the formula##STR45## wherein D¹ and m are as hereinbefore set forth in the presenceof a solvent such as DMF, methylene chloride or ether and in thepresence of a catalyst such as 4-(dimethylamino)pyridine and an aid forforming esters at low temperatures. Representative of such agents arecarbodiimides such as dicyclohexylcarbodiimide.

The desired product can be separated from the reaction mixture of theabove preparative procedures employing conventional separatoryprocedures known to those skilled in the art including steps of solventextraction, filtration, water washing, column chromatography,neutralization, acidification, crystallization and distillation.

The preparation of the optical isomer forms of the active compounds ofthe present invention follow conventional procedures employed to preparerelated compounds. Such procedures include those taught in U.S. patentapplication Ser. No. 4,532,328; European Patent Applications 2,800,3,890 and 6,608; German OLS 2,949,728 and U.K. Patent Application GB2,042,503A. The teachings of these applications are incorporated hereinby reference thereto.

Since the hereinabove and hereinafter set forth compound preparationprocedures employ only standard chemistry practices, and it is knownthat slightly different reactants can require slightly differentreaction parameters from those for other reactants, it is to beunderstood that minor modifications to the reaction parameters set forthsuch as the use of an excess of one reactant, the use of a catalyst, theuse of high temperature and/or pressure equipment, high speed mixing andother such conventional changes are within the scope of this invention.

Preparation of Starting Materials

The 4-((aryloxy)phenoxy)alkenols employed herein as starting materialsand corresponding to the formula ##STR46## are for the most part knowncompounds and can be prepared employing known techniques includingreducing carboxylic acids and their esters which correspond to theformula ##STR47## wherein in Formulae II or VIII; Ar, Y, Y¹, R, T and R⁴are as hereinbefore defined.

Representative compounds of Formula II can be found in U.S. Pat. Nos.3,946,084; 4,267,317 and 4,360,375; European Patent Applications 10,232;42,750; 46,467; 46,468 and 47,972; West German DE OF 2,926,607 andChemical Abstracts 94:83960C wherein such compounds and theirpreparation are taught.

Representative compounds of Formula VIII can be found in U.S. Pat. Nos.3,900,507; 4,163,661; 4,216,007; 4,263,040; 4,360,375 and 4,368,068;Japan Kokai 79-109,915; 81-43,269; 81-57,769; 81-63,968; 81-75,405 and81-67,671; West German DE OF 2,926,607 and 2,948,095 and European PatentApplications 42,750; 46,467; 46,468 and 47,972 wherein such compoundsand their preparations are taught.

Many of the compounds of Formulae II and VIII which are not specificallytaught in the above-cited references can be prepared using theprocedures of these references and employing the appropriate startingmaterials. These references are incorporated herein by referencethereto.

Additionally, the compounds of Formulae II and VIII can be prepared bythe reaction of an appropriate arylhalide corresponding to the formula

    Ar--X.sup.1                                                (IX)

wherein Ar is as hereinbefore defined and X¹ represents --Br, --Cl or--F and an appropriate hydroxyphenoxyalkenol or hydroxyphenoxy alkenylcarboxylic acid or ester corresponding to the formula ##STR48## whereinY, Y¹, R and T are as hereinbefore defined and R⁸ is --CH₂ OH or--COOR⁴. In carrying out this reaction, the reactants and a strong basesuch as an anhydrous alkali metal hydride, alkoxide, hydroxide orcarbonate are mixed together in a dipolar, aprotic solvent such as, forexample, dimethylformamide (DMF), acetone, methyl ethyl ketone,acetonitrile, dimethylsulfoxide (DMSO), sulfolane, N-methylpyrrolidoneor the like. The reaction is advantageously carried out at elevatedtemperatures of from about 50° to 120° C. This procedure is also thepreferred procedure to use when Ar is quinoxalinyl or pyrimidinyl.

The compounds of Formulae II and VIII wherein Y and Y¹ are both hydrogencan also be prepared by the reaction of an appropriate aryloxyphenolcorresponding to the formula ##STR49## with an appropriate α-haloalkenolor α-haloalkenoic acid or ester corresponding to the formula ##STR50##wherein Ar, Y, Y¹, Hal, R, T and R⁸ are as hereinbefore definedemploying the same reaction conditions as set forth hereinabove for thereaction between the reactants of Formulae IX and X. This is not apreferred procedure to employ when Y and/or Y¹ are fluorine due to anincrease in the number of isomers present during the preparation of thecompound of Formula XI.

The hydroxyphenoxy alkenols, carboxylic acid or esters corresponding tothe formula ##STR51## are prepared by a variety of procedures. Thosecompounds wherein Y and Y¹ are both hydrogen, are for the most partknown compounds and are taught in U.S. Pat. Nos. 4,216,007; 4,267,317and 4,368,068; European Patent Applications 3,890; 46,467 and 46,468;and Japanese Kokai 80-79,344; 81-59,725 and 81-59,718.

Those compounds wherein Y and/or Y¹ are fluorine can be prepared in amultistep procedure as follows: ##STR52## No attempt has been made topresent a balanced equation in the above reaction sequence.

The above reaction steps can be carried out as follows:

Step A

The appropriate fluorophenol of Formula XIII in a solvent such as, forexample, methylene chloride, is reacted for from about 1 to about 3hours with 90 percent nitric acid at a temperature of from about -15° C.to about 5° C. At the end of this period, the desired 2-fluoro- or2,6-difluoro-4-nitrophenol product of Formula XIV is recovered employingconventional procedures.

Step B

The thus formed 2-fluoro- or 2,6-difluoro-4-nitrophenol of Formula XIVis reacted with an appropriate α-haloalkenoic acid or estercorresponding to Formula XIIa. In carrying out this reaction, the phenolcompound, the compound of Formula XIIa and a metallic base such assodium or potassium carbonate, or an organic base such as triethylamineare mixed together in the presence of a solvent such asdimethylsulfoxide (DMSO), dimethylformamide, tetrahydrofuran,acetonitrile, hexamethylphosphoramide or N-methylpyrrolidone and heatedto a temperature between about 40° C. to about 220° C. The desiredfluorinated 4-nitrophenoxy alkenol, acid or ester corresponding toFormula XV is recovered employing conventional procedures.

Step C

The thus formed fluorinated 4-nitrophenoxyalkenoic, acid or estercorresponding to Formula XV is selectively reduced to the correspondingamino (aniline) compound corresponding to Formula XVI. This reductioncan be conveniently carried out employing conventional stannous chloridereduction procedures. The product is recovered employing conventionalrecovery procedures.

Step D

The thus formed aniline compound corresponding to Formula XVI is treatedwith an aqueous solution of concentrated HCl at a temperature of fromabout 0°-10° C. and this solution is then reacted with an aqueoussolution of sodium nitrite. This mixture is thereafter reacted with anaqueous solution of fluoroboric acid to form the desired correspondingdiazonium tetrafluoroborate compound corresponding to Formula XVII. Theproduct is separated employing conventional procedure.

Step E

The thus formed compound corresponding to Formula XVII is treated underreflux conditions with a mixture of an alkali metal trifluoroacetate intrifluoroacetic acid followed by conventional acidification (if the freeacid form is desired) to obtain the desired compound corresponding toFormula X.

The halides employed as starting materials and corresponding to theformula

    Hal--R.sup.7                                               (III)

wherein Hal and R⁷ are as hereinbefore defined are for the most partknown in the chemical literature and/or commercially produced compounds.

In addition, those compounds not specifically taught or produced can beprepared by procedures analogous to those employed to prepare the taughtor produced compounds employing the appropriate starting materials.

The ester compounds corresponding to the formula ##STR53## are wellknown in the chemical literature.

The aromatic/heterocyclic halides employed as starting materials andwhich correspond to the formula

    Ar--X.sup.1                                                (IX)

wherein Ar and X¹ are as hereinbefore defined, are all known and/orcommercially produced compounds and for the most part are taught in theabove-listed applications and/or patents which teach preparing compoundsof Formulae II and VIII. In addition, compounds of Formula IX notspecifically taught can be prepared by procedures analogous to those ofthe above references employing the appropriate starting materials.

The α-haloalkenoic acid or esters employed as starting materials andcorresponding to the formula ##STR54## wherein Hal, R, T and R⁴ are ashereinbefore defined are all known compounds and such compounds aretaught in U.S. Pat. Nos. 4,163,661; 4,216,007; 4,263,040 and 4,360,375and European Patent Application 42,750, among others.

The following examples illustrate the present invention and the mannerby which it can be practiced but, as such, are not to be construed aslimitations upon the overall scope thereof.

The compounds obtained in the following examples were generallycharacterized by infrared and nuclear magnetic resonance spectrometry.

EXAMPLE 1

E isomer of 4-(4-hydroxyphenoxy)-2-penten-1-ol ##STR55##

An oven-dried flask was equipped with a nitrogen inlet, a stirrer, athermometer and a septum stoppered dropping funnel and was flushed withnitrogen. The flask was charged with a solution of 26.6 grams (g) (120millimole (mmol)) of methyl (E)-4-(4-hydroxyphenoxy)-2-pentenoate in 150milliliters (ml) of toluene. The solution was cooled to -78° C., and thedropping funnel was charged with 250 ml (375 mmol) of 25 percent (%)solution of diisobutylaluminum hydride (DIBAL) in toluene. The DIBALsolution was then added at -78° C. dropwise to the reaction mixture overa 1.5 hour period, and the reaction was stirred at -78° C. for anadditional 0.5 hour. The reaction was quenched by cautious, dropwiseaddition of 250 ml of a stock solution prepared from 6 parts of water,25 parts of acetic acid and 75 parts of ether while maintaining thetemperature below -50° C. The resulting mixture was allowed to warm toroom temperature and filtered, and the solid was washed with ether. Thefiltrates were combined and reserved while the solid was partitionedbetween water and ether.

This mixture was made acidic with aqueous HCl, and the ether layerseparated and combined with the reserved filtrates. The combined organicsolution was then washed to neutrality with saturated aqueous sodiumbicarbonate, dried over MgSO₄ and evaporated to dryness. The oilyresidue was then purified by preparative scale liquid chromatography(HPLC) eluting with 3:2 hexane: acetone. Removal of solvent and thoroughdrying left 19.3 g (83%) of the desired alcohol as a tan oil.

    ______________________________________                                        Elemental Analysis:                                                                              % C  % H                                                   ______________________________________                                        Calculated for C.sub.11 H.sub.14 O.sub.3 :                                                         68.02  7.26                                              Found:               67.24  7.26                                              ______________________________________                                    

EXAMPLE 2 E isomer of4-(4-((6-chloro-2-quinolinyl)oxy)phenoxy)-2-penten-1-ol ##STR56##

A mixture of 1.58 g (8 mmol) of 2,6-dichloroquinoline, 1.75 g (9 mmol)of (E)-4-(4-hydroxyphenoxy)-2-penten-1-ol, 1.52 g (11 mmol) of powdered,anhydrous potassium carbonate and 30 ml of dry dimethylsulfoxide waswarmed under nitrogen at 110° C. for a period of 5 hours. The mixturewas cooled to room temperature, poured into ice cold 1 percent aqueoussodium hydroxide, and the resulting aqueous mixture was extracted threetimes with ether. The combined ether layers were washed once with 1percent aqueous sodium hydroxide and twice with water, dried over MgSO₄and evaporated to dryness. The residue was purified by preparative scaleHPLC, eluting with 7:3 hexane:ethyl acetate, and then thoroughly driedto leave 1.71 g (60%) of desired pentenol as a yellow, viscous gum.

EXAMPLE 3 E isomer of4-(4-((6-chloro-2-quinoxalinyl)oxy)phenoxy)-2-penten-1-ol ##STR57##

A mixture of 1.99 g (10 mmol) of 2,6-dichloroquinoxaline, 2.13 g (11mmol) of (E)-4-(4-hydroxyphenoxy)-2-penten-1-ol, 1.73 g (12.5 mmol) ofpowdered, anhydrous potassium carbonate and 50 ml of dry acetonitrilewas warmed at reflux under nitrogen for a period of 3 hours. The mixturewas cooled to room temperature, and the solid filtered off and washedwell with ether. The filtrates were combined and evaporated to dryness,and the residue partitioned between ether and 2 percent aqueous sodiumhydroxide. The aqueous layer was separated and extracted again withether. The combined organic layers were washed with water, dried overMgSO₄ and evaporated to dryness. The residual solid was purified bypreparative scale HPLC, eluting with 7:3 hexane: ethyl acetate, to givea solid which was recrystallized from toluene. This gave 2.60 g (73%) ofthe desired pentenol as pale yellow crystals, having a melting point(m.p.) of 124°-126° C.

    ______________________________________                                        Elemental Analysis:                                                                            % C     % H    % N                                           ______________________________________                                        Calculated for C.sub.19 H.sub.17 ClN.sub.2 O.sub.3 :                                             63.95     4.80   7.85                                      Found:             63.73     4.75   7.81                                      ______________________________________                                    

EXAMPLE 4 E isomer of4-(4-((5-iodo-2-pyrimidinyl)oxy)phenoxy)-2-penten-1-ol ##STR58##

A mixture of 1.68 g (7 mmol) of 2-chloro-5-iodopyrimidine, 1.55 g (8mmol) of (E)-4-(4-hydroxyphenoxy-2-penten-1-ol, 1.24 g (9 mmol) ofpowdered, anhydrous potassium carbonate and 35 ml of dry acetonitrilewas stirred under nitrogen at reflux for a period of 3 hours. Themixture was cooled and filtered, and the filtered solid was thoroughlywashed with ether. The filtrates were combined and evaporated todryness, and the residue partitioned between ether and 1 percent aqueoussodium hydroxide. The aqueous layer was separated and again extractedwith ether. The combined organic layers were washed twice with water,dried over MgSO₄ and evaporated to dryness. The residual oil waspurified by preparative scale HPLC, and then dried in a Kugelrohrapparatus at 55° C. and 0.1 mm Hg for 1 hour. This left 2.75 g(quantitative) of the desired pentenol as a pale yellow, viscous gum.

    ______________________________________                                        Elemental Analysis:                                                                            % C     % H    % N                                           ______________________________________                                        Calculated for C.sub.15 H.sub.15 IN.sub.2 O.sub.3 :                                              45.24     3.80   7.04                                      Found:             44.70     3.67   6.78                                      ______________________________________                                    

EXAMPLE 5

Step A E isomer of4-(4-((3-chloro-5-(trifluoromethyl)-2-pyridinyl)oxy)phenoxy-2-pentenoicacid, methyl ester ##STR59##

A mixture of 28.95 g (0.1 mol) of4-((3-chloro-5-(trifluoromethyl)-2-pyridinyl)oxy)phenol, 16.56 g (0.12mol) of powdered, anhydrous potassium carbonate and 250 ml of dryacetonitrile was warmed at reflux under nitrogen for 1.5 hours. Themixture was cooled to room temperature and 20.27 g (0.105 mol) of methyl(E)-4-bromo-2-pentenoate was added. The resulting mixture was maintainedat reflux for 2.5 hours and then cooled to room temperature andfiltered. The filtered solid was washed with ether, and the combinedfiltrates evaporated to dryness on a rotovap. The residual oil was takenup in ether, and the organic solution washed twice with water, twicewith 5 percent aqueous sodium hydroxide solution and again with water,dried over MgSO₄ and evaporated on a rotovap. The residual solid wascrystallized twice from hexane to give nearly colorless crystals of thedesired pentenoate product. The filtrates from the recrystallizationwere combined and filtered through silica gel, eluting with CH₂ Cl₂.Removal of solvent under vacuum left a colorless solid which wasrecrystallized from hexane to give additional pentenoate product. Totalyield was 27.24 g (68%) of colorless crystals melting at 88°-90° C.

    ______________________________________                                        Elemental Analysis:                                                                            % C     % H    % N                                           ______________________________________                                        Calculated for C.sub.18 H.sub.15 ClF.sub.3 NO.sub.4                                              53.81     3.76   3.49                                      Found:             53.65     3.49   3.43                                      ______________________________________                                    

Step B E isomer of4-(4-((3-chloro-5-(trifluoromethyl)-2-pyridinyl)oxy)phenoxy)-2-penten-1-ol##STR60##

An oven-dried flask was equipped with a thermometer, a nitrogen inlet, amagnetic stirrer and a dropping funnel and flushed with nitrogen. Theflask was charged with 20.08 g (0.05 mol) of(E)-4-(4((3-chloro-5-(trifluoromethyl)-2-pyridinyl)oxy)phenoxy-2-pentenoicacid, methyl ester and 150 ml of toluene, and the addition funnel wasstoppered with a rubber septum The solution was cooled to -78° C., andthe addition funnel charged with 70 ml (0.105 mol) of 25 percentdiisobutylaluminumhydride (DIBAL) in toluene. The DIBAL was then addeddropwise to the reaction solution at such a rate that the temperatureremained <-60° C. Upon completion of the addition, the solution wasmaintained at -78° C. for 30 minutes, and then 70 ml of a stock solutionprepared from 6 ml of water, 25 ml of glacial acetic acid and 75 ml ofether was placed in the dropping funnel and added dropwise over 30minutes to the reaction mixture. The mixture was then allowed to warm toroom temperature, and the alumina gel filtered off and washed well withether. The combined filtrates were washed with dilute aqueous HCl,saturated aqueous sodium bicarbonate, dried over MgSO₄ and evaporated todryness on a rotovap. The residual oil was purified by preparative scaleHPLC, eluting with 7:3 hexane:ethyl acetate. The resulting nearlycolorless viscous oil was dried on the rotovap at 65° C. and about 1 mmHg vacuum for 1.5 hours. Total yield of the desired pentenol product was16.41 g (88%).

    ______________________________________                                        Elemental Analysis:                                                                            % C     % H    % N                                           ______________________________________                                        Calculated for C.sub.17 H.sub.15 ClF.sub.3 NO.sub.3                                              54.63     4.05   3.75                                      Found:             54.09     3.85   3.67                                      ______________________________________                                    

By following the procedures of Examples 1-4 (Method A) and Example 5(Method B), employing the appropriate starting phenols, the followingalkenols are prepared.

                  TABLE 6                                                         ______________________________________                                         ##STR61##                                                                                            Molecular Formula and                                 Meth-            M.P.   Elemental Analysis                                    od    Ar             °C. % C  % H  % N                                 ______________________________________                                               ##STR62##     94- 97 C.sub.17 H.sub.15 ClN.sub.2 O.sub.3 S                                         Calc:56.274.177.72 Found:55.984.077.75            ______________________________________                                    

EXAMPLE 6 E isomer of4-(4-((6-chloro-2-quinolinyl)oxy)phenoxy-2-penten-1-ol,1-methylethylsulfonate ##STR63##

A solution prepared from 1.07 g (3 mmol) of the pentenol obtained inExample 2, 0.40 g (4 mmol) of triethylamine, and 20 ml of methylenechloride was cooled at 0° C. under nitrogen and a solution of 0.50 g(3.5 mmol) of isopropylsulfonylchloride in 3 ml of methylene chloridewas added in one portion. The resulting solution was stirred at 0° C.for 30 minutes and then poured into a mixture of ether and about 1Naqueous HCl. The organic layer was separated, dried over MgSO₄ andevaporated to dryness. The residue was purified by preparative scaleHPLC, eluting with 3:1 hexane:ethyl acetate, and then dried in aKugelrohr apparatus at 50° C. and 0.1 mm Hg for 1 hour. This left 1.31 g(95%) of desired sulfonate product as a viscous oil. (Compound 1).

    ______________________________________                                        Elemental Analysis:                                                                            % C     % H    % N                                           ______________________________________                                        Calculated for C.sub.23 H.sub.24 ClNO.sub.5 S:                                                   59.80     5.24   3.03                                      Found:             58.91     5.11   2.90                                      ______________________________________                                    

EXAMPLE 7 E isomer of4-(4-((6chloro-2-quinoxalinyl)oxy)-phenoxy)-2-penten-1-ol, 1-methylethylsulfonate ##STR64##

A solution prepared from 1.78 g (5 mmol) of the pentenol obtained inExample 3 above, 0.61 g (6 mmol) of triethylamine and 25 ml of methylenechloride was cooled under N₂ at 0° C. while 0.78 g (5.5 mmol) ofisopropylsulfonylchloride was added in one portion. After stirring at 0°C. for 45 minutes, the mixture was poured into a mixture of ether andwater. The organic layer was separated, dried over MgSO₄ and evaporatedto dryness. The residual solid was taken up in boiling hexane, filteredwhile hot and allowed to cool to give pale yellow crystals. The crystalswere filtered and dried to give 1.65 g (71%) of the desired sulfonateproduct, m p. 95°-96° C. (Compound 2).

    ______________________________________                                        Elemental Analysis:                                                                             % C    % H    % N                                           ______________________________________                                        Calculated for C.sub.22 H.sub.23 ClN.sub.2 O.sub.5 S:                                             57.07    5.01   6.05                                      Found:              56.78    4.92   5.96                                      ______________________________________                                    

EXAMPLE 8 E isomer of4-(4-((5-iodo-2-pyrimidinyl)oxy)phenoxy)-2-penten-1-ol,(1-methylethyl)sulfonate ##STR65##

A solution prepared from 1.59 g (4 mmol) of the pentenol obtained inExample 4 above, 0.51 g (5 mmol) of triethylamine and 25 ml of methylenechloride was stirred under nitrogen at 0° C. while a solution of 0.63 g(4.4 mmol) of isopropylsulfonylchloride in 3 ml of methylene chloridewas slowly added. The resulting solution was stirred at 0° C. for 1 hourand then poured into a mixture of ice cold 1N aqueous HCl and ether. Theorganic layer was separated, dried over MgSO₄ and evaporated to dryness.The residual oil was purified by preparative scale HPLC, eluting with3:1 hexane:ethyl acetate, and then dried in a Kugelrohr apparatus atabout 0.2 mm Hg. This left 1.78 g (88%) of the desired sulfonate productas a straw-colored, viscous oil. (Compound 3).

    ______________________________________                                        Elemental Analysis:                                                                            % C     % H    % N                                           ______________________________________                                        Calculated for C.sub.18 H.sub.17 IN.sub.2 O.sub.5 S:                                             42.86     4.20   5.56                                      Found:             42.01     4.11   5.26                                      ______________________________________                                    

EXAMPLE 9 E isomer of4-(4-((3-chloro-5-(trifluoromethyl)-2-pyridinyl)oxy)phenoxy)-2-penten-1-ol,methane sulfonate ##STR66##

A solution prepared from 5.60 g (15 mmol) of(E)-4-(4-((3-chloro-5-(trifluoromethyl)-2-pyridinyl)oxy)phenoxy)-2-penten-1-ol(prepared as in Step B of Example 5), 1.62 g (16 mmol) of triethylamineand 100 ml of methylene chloride was stirred at 0° C. under N₂ while asolution of 1.83 g (16 mmol) of methane sulfonylchloride in 10 ml ofmethylene chloride was added in portions over 30 minutes. The resultingsolution was stirred at 0° C. for 30 minutes and then at ambienttemperature for 30 minutes and finally poured into ice cold 1N aqueousHCl. The organic layer was separated, dried over MgSO₄ and evaporated todryness. The residual oil was purified by preparative scale HPLC,eluting with 3:1 hexane:ethyl acetate, and then dried on a rotovap at65° C. and about 1 mm Hg for 1.5 hours to give 5.82 g (85%) of desiredproduct as a colorless viscous oil. Upon standing for one week in thehood, the oil solidified, and seed crystals were collected. Theremaining material was taken up in a mixture of ethyl acetate andhexane, the seed crystals added and the mixture stirred. Colorlesscrystalline product precipitated and was filtered off and washed withhexane. The crystalline product melted at 64°-65° C. (Compound 4).

    ______________________________________                                        Elemental Analysis:                                                                             % C    % H    % N                                           ______________________________________                                        Calculated for C.sub.18 H.sub.17 ClF.sub.3 NO.sub.5 S:                                            47.84    3.79   3.10                                      Found:              48.09    3.55   3.11                                      ______________________________________                                    

EXAMPLE 10 E isomer of4-(4-((3-chloro-5-(trifluoromethyl)-2-pyridinyl)oxy)phenoxy)-2-penten-1-ol,(1-methylethyl)sulfonate ##STR67##

A solution of 2.24 g (6 mmol) of the pentenol obtained in Step B ofExample 5, 0.71 g (7 mmol) of triethylamine and 50 ml of methylenechloride was stirred under N₂ at 0° C. while a solution of 1.00 g (7mmol) of isopropylsulfonylchloride in 3 ml of CH₂ Cl₂ was added inportions. The solution was then allowed to warm slowly to 20° C. andthen poured into a mixture of 1 percent aqueous HCl and ether. Theaqueous layer was separated and extracted with ether. The combinedorganic layers were washed twice with water, dried over MgSO₄ andevaporated to dryness. The residual oil was purified by preparativescale HPLC, eluting with 4:1 hexane:ethyl acetate, and then dried on therotovap at 55° C. and about 1 mm Hg for 2 hours. This gave 2.39 g (83%)of desired product as a colorless, viscous gum. (Compound 5).

    ______________________________________                                        Elemental Analysis:                                                                             % C    % H    % N                                           ______________________________________                                        Calculated for C.sub.20 H.sub.21 ClF.sub.3 NO.sub.5 S:                                            50.05    4.41   2.92                                      Found:              49.43    4.30   2.80                                      ______________________________________                                    

EXAMPLE 11 E isomer of4-(4-((3-chloro-5-(trifluoromethyl)-2-pyridinyl)oxy)phenoxy)-2-penten-1-ol,N-(1-methylethyl)sulfamate ##STR68##

A solution prepared from 1.87 g (5 mmol) of the pentenol obtained inStep B of Example 5, 0.61 g (6 mmol) of triethylamine and 50 ml ofmethylene chloride was stirred at 0° C. under N₂ while a solution of0.87 g (5.5 mmol) of isopropylsulfamoyl chloride in 2 ml of methylenechloride was added in one portion. The resulting solution was stirred at0° C. for 45 minutes and then poured into a mixture of ice cold 1Naqueous HCl and ether. The organic layer was separated, dried over MgSO₄and evaporated to dryness. The residual oil was purified by preparativescale HPLC, eluting with 3:1 hexane:ethyl acetate, and then dried in aKugelrohr apparatus at 55° C. and 0.1-0.2 mm Hg for 1 hour. This left2.35 g (95%) of desired sulfamate product as a pale yellow, viscous oil.(Compound 6).

    ______________________________________                                        Elemental Analysis:                                                                            % C     % H    % N                                           ______________________________________                                        Calculated for C.sub.20 H.sub.22 ClF.sub.3 N.sub.2 O.sub.5 S:                                    48.53     4.48   5.66                                      Found:             48.44     4.39   5.64                                      ______________________________________                                    

By following the procedure of Examples 6-12 employing the appropriatestarting pentenols and sulfonyl or sulfamoyl halides, the followingcompounds in Table 7 are prepared.

                                      TABLE 7                                     __________________________________________________________________________     ##STR69##                                                                                                      Molecular Formula and                       Compound                          Elemental Analysis                          No.   Ar            R.sup.2  M.P. °C.                                                                        % C                                                                              % H                                                                              % N                               __________________________________________________________________________                                      C.sub.22 H.sub.24 ClN.sub.3 O.sub.5 S              ##STR70##    NHCH(CH.sub.3).sub.2                                                                   73-75                                                                              Calc: Found:                                                                      55.28 55.59                                                                      5.06 5.09                                                                        8.79 8.68                                                           C.sub.20 H.sub.19 ClN.sub.2 O.sub.5 S       8                                                                                    ##STR71##    CH.sub.3 115-116                                                                            Calc: Found:                                                                      55.23 54.94                                                                      4.40 4.30                                                                        6.44 6.34                                                           C.sub.21 H.sub.21 ClN.sub.2 O.sub.5 S       9                                                                                    ##STR72##    C.sub.2 H.sub.5                                                                        95-97                                                                              Calc: Found:                                                                      56.18 56.27                                                                      4.72 4.58                                                                        6.24 6.14                                                           C.sub.22 H.sub.23 ClN.sub.2 O.sub.5 S       10                                                                                   ##STR73##    C.sub.3 H.sub.7                                                                        81-83                                                                              Calc: Found:                                                                      57.07 56.44                                                                      5.01 4.91                                                                        6.05 5.94                                                           C.sub.23 H.sub.25 ClN.sub.2 O.sub.5 S       11                                                                                   ##STR74##    C.sub.4 H.sub.9                                                                        85-87                                                                              Calc: Found:                                                                      57.91 57.89                                                                      5.28 5.16                                                                        5.87 5.71                         __________________________________________________________________________

EXAMPLE 12 E isomer of4-(4-((6-chloro-2-quinoxalinyl)oxy)phenoxy)-2-penten-1-ol, acetate##STR75##

To an ice-cooled nitrogen flushed solution of 1.78 g (5 mmol) of thepentenol obtained, in Example 3 above in 10 ml of pyridine was added0.61 g (6 mmol) of acetic anhydride. The resulting solution was allowedto warm to room temperature and stirred under nitrogen overnight. Thesolution was then poured into a mixture of ether and water. The organiclayer was separated and washed three times with 2 percent aqueous HCland saturated aqueous NaHCO₃, dried over MgSO₄ and evaporated to leavean off-white solid. The solid was purified by filtration, usingmethylene chloride as the solvent, through a short plug of silica gel,and then, after removal of solvent, recrystallized frommethylcyclohexane. This gave colorless crystals which were filtered,washed with hexane and dried to give 1.27 g (64%) of the desired acetateas colorless crystals, m.p. 89°-90° C. (Compound 12).

    ______________________________________                                        Elemental Analysis:                                                                            % C     % H    % N                                           ______________________________________                                        Calculated for C.sub.21 H.sub.19 ClN.sub.2 O.sub.4 :                                             63.24     4.80   7.03                                      Found:             62.49     4.70   6.89                                      ______________________________________                                    

By following the procedures of Example 13 employing the appropriatestarting pentenols and acid anhydride, the following compounds in Table8 are prepared.

                                      TABLE 8                                     __________________________________________________________________________     ##STR76##                                                                                            Molecular Formula and                                 Compound                Elemental Analysis                                    No.   Ar          Condition % C                                                                              % H                                                                              % N                                         __________________________________________________________________________                            C.sub.19 H.sub.17 ClN.sub.2 O.sub.4 S                 13                                                                                   ##STR77##  thick gum                                                                           Calc: Found:                                                                      56.36 55.96                                                                      4.23 4.20                                                                        6.92 7.29                                   __________________________________________________________________________

EXAMPLE 13 E isomer of4-(4-((6-chloro-2-quinoxalinyl)oxy)phenoxy)-2-penten-1-ol, benzoate##STR78##

A nitrogen flushed solution of 1.78 g (5 mmol) of the pentenol obtainedin Example 3 in 20 ml of pyridine was cooled in an ice bath and 0.77 g(5.5 mmol) of benzoylchloride was slowly added. The resulting mixturewas stirred at 0° C. for 1 hour and then at ambient temperature for 2hours. The reaction mixture was then poured into a mixture of water andether. The organic layer was separated, washed twice with 1N aqueous HCland then with saturated aqueous NaHCO₃, dried over MgSO₄ and evaporatedto dryness. After standing at room temperature, the residue slowlycrystallized and the solid recrystallized from methylcyclohexane togive, after filtering and drying, 1.90 g (82%) of the desired benzoateas colorless crystals melting at 79°-81° C. (Compound 14).

    ______________________________________                                        Elemental Analysis:                                                                            % C     % H    % N                                           ______________________________________                                        Calculated for C.sub.26 H.sub.21 ClN.sub.2 O.sub.4 :                                             67.75     4.59   6.08                                      Found:             67.56     4.49   6.08                                      ______________________________________                                    

By substantially following the procedures of Example 14 employing theappropriate starting pentenols and acid halide in pyridine, thefollowing compounds in Table 9 are prepared.

                                      TABLE 9                                     __________________________________________________________________________     ##STR79##                                                                                                   M.P. °C. or                                                                  Molecular Formula and                    Compound                       Physical                                                                            Elemental Analysis                       No.   Ar            R.sup.2    State     % C                                                                              % H                                                                              % N                            __________________________________________________________________________    15                                                                                   ##STR80##    C(CH.sub.3).sub.3                                                                        86-88 C.sub.24 H.sub.25 ClN.sub.2 O.sub.4                                           Calc:65.375.726.35 Found:65.395.726.2                                         8                                        16                                                                                   ##STR81##                                                                                   ##STR82## thick gum                                                                           C.sub.24 H.sub.19 ClN.sub.2 O.sub.4                                           S Calc:61.734.106.00 Found:62.064.23                                          .02                                      17                                                                                   ##STR83##                                                                                   ##STR84## thick gum                                                                           C.sub.24 H.sub.19 ClF.sub.3 NO.sub.4                                          alc:60.324.012.93 Found:60.403.972.93                                         .                                        18                                                                                   ##STR85##                                                                                   ##STR86## 71-75 C.sub.27 H.sub.20 ClF.sub.3 N.sub.2                                           O.sub.4 Calc:61.313.815.30 Found:61.3                                         23.825.61                                19                                                                                   ##STR87##    CH(CH.sub.3).sub.2                                                                       45-49 C.sub.23 H.sub.23 ClN.sub.2 O.sub.4                                           Calc:64.715.436.56 Found:64.515.376.6                                         3                                        20                                                                                   ##STR88##    C.sub.3 H.sub.7                                                                          yellow oil                                                                          C.sub.23 H.sub.23 ClN.sub.2 O.sub.4                                           Calc:64.715.436.56 Found:64.555.466.7                                         6                                        21                                                                                   ##STR89##                                                                                   ##STR90## 80-84 C.sub.27 H.sub.20 ClF.sub.3 N.sub.2                                           O.sub.5 Calc:59.513.705.14 Found:59.1                                         03.685.29                                22                                                                                   ##STR91##                                                                                   ##STR92## 70-74 C.sub.27 H.sub.23 ClN.sub.2 O.sub.4                                           Calc:68.284.885.90 Found:68.635.045.5                                         0                                        23                                                                                   ##STR93##                                                                                   ##STR94## 87-89 C.sub.28 H.sub.25 ClN.sub.2 O.sub.4                                           Calc:68.785.155.73 Found:68.595.205.9                                         2                                        24                                                                                   ##STR95##                                                                                   ##STR96##  99-103                                                                             C.sub.26 H.sub.20 ClN.sub.3 O.sub.6                                           Calc:61.733.988.31 Found:62.134.118.2                                         8                                        __________________________________________________________________________

EXAMPLE 14 E isomer of4-(4-((6-chloro-2-quinoxalinyl)oxy)phenoxy)-2-penten-1-ol,4-chlorobenzoate ##STR97##

A nitrogen flushed solution of 1.78 g (5 mmol) of the pentenol obtainedin Example 3 above, 0.61 g (6 mmol) of triethylamine and 40 ml ofmethylene chloride was cooled in an ice bath. A solution of 1.05 g (6mmol) of 4-chlorobenzoyl chloride in 2 ml of methylene chloride wasslowly added, and the resulting solution allowed to stir at ambienttemperature overnight. The mixture was then poured into water, and theorganic layer separated and washed with saturated aqueous NaHCO₃ andsaturated aqueous NaCl, dried over MgSO₄ and evaporated to leave an oil.The oil was purified by preparative scale HPLC, eluting with 85:15hexane:ethyl acetate. After removal of the solvent, an oil was obtainedwhich, after trituration with hexane, solidified. The solid wasfiltered, washed with hexane and dried to give 1.91 g (77%) of thedesired ester melting at 96°-99° C. (Compound 25).

    ______________________________________                                        Elemental Analysis:                                                                            % C     % H    % N                                           ______________________________________                                        Calculated for C.sub.26 H.sub.20 Cl.sub.2 N.sub.2 O.sub.4 :                                      63.04     4.07   5.66                                      Found:             62.41     3.99   5.71                                      ______________________________________                                    

By following the procedures of Example 15 employing the appropriatestarting pentenols and acid chloride, the following compounds in Table10 are prepared.

                                      TABLE 10                                    __________________________________________________________________________     ##STR98##                                                                                                M.P. °C. or                                                                  Molecular Formula and                       Compound                    Physical                                                                            Elemental Analysis                          No.   Ar            R.sup.2 State     % C                                                                              % H                                                                              % N                               __________________________________________________________________________    26                                                                                   ##STR99##                                                                                   ##STR100##                                                                           63-65 C.sub.26 H.sub.20 Cl.sub.2 N.sub.2                                            O.sub.4 Calc:63.044.075.66 Found:62.534.                                      075.64                                      27                                                                                   ##STR101##                                                                                  ##STR102##                                                                           thick gum                                                                           C.sub.26 H.sub.20 Cl.sub.2 N.sub.2                                            O.sub.4 Calc:63.044.075.66 Found:62.123.                                      905.52                                      28                                                                                   ##STR103##                                                                                  ##STR104##                                                                           107-110                                                                             C.sub.26 H.sub.19 Cl.sub.3 N.sub.2                                            O.sub.4 Calc:58.943.615.29 Found:58.833.                                      535.11                                      __________________________________________________________________________

EXAMPLE 15 4-(Aminocarbonyl)benzoic acid,4-(4-((6-chloro-2-quinoxalinyl)oxy)phenoxy)-2-pentenyl ester ##STR105##

A mixture of 1.5 g (4.2 mmol) of the pentenol obtained in Example 3above, 1.04 g (6.3 mmol) of 4-(aminocarbonyl)benzoic acid, 1.30 g (6.3mmol) of dicyclohexylcarbodiimide (DCC), 0.05 g of4-(dimethylamino)pyridine and 20 ml of DMF was stirred at roomtemperature overnight. An additional 0.3 g of DCC and 0.25 g of4-(aminocarbonyl)benzoic acid were added and the mixture was stirred anadditional 20 hours. The mixture was then poured into ether, water addedand filtered. The filtrates were separated, and the organic layer washedwith saturated aqueous NaHCO₃ and water, dried over MgSO₄ and evaporatedto dryness. The residue was purified by preparative scale HPLC, elutingwith a 3:2 hexane:acetone mixture to give 0.55 g of the desired productas a tan, glassy solid, m.p. 144°-148° C. (Compound 29).

    ______________________________________                                        Elemental Analysis:                                                                            % C     % H    % N                                           ______________________________________                                        Calculated for C.sub.27 H.sub.22 ClN.sub.3 O.sub.5 :                                             64.35     4.40   8.34                                      Found:             63.97     4.70   8.06                                      ______________________________________                                    

EXAMPLE 16 4-(Acetylamino)benzoic acid,4-(4-((6-chloro-2-quinoxalinyl)oxy)phenoxy)-2-pentenyl ester ##STR106##

A mixture of 1.5 g (4.2 mmol) of the pentenol obtained in Example 3above, 0.82 g (4.6 mmol) of 4-(acetylamino)benzoic acid, 0.95 g (4.6mmol) of dicyclohexylcarbodiimide and 0.05 g of4-(dimethylamino)pyridine in 20 ml of dimethylformamide was stirred atroom temperature for 72 hours. The mixture was diluted with ether andwater and filtered. The filtrates were separated, and the organic layerwashed with saturated aqueous NaHCO₃ and water, dried over MgSO₄ andevaporated to dryness. The residue was purified by preparative scaleHPLC, eluting with a 65:35 hexane:acetone mixture to give 0.6 g of thedesired product as a pale yellow, glassy solid, m.p. 62°-68° C.(Compound 30).

    ______________________________________                                        Elemental Analysis:                                                                            % C     % H    % N                                           ______________________________________                                        Calculated for C.sub.28 H.sub.24 ClN.sub.3 O.sub.5 :                                             64.93     4.67   8.11                                      Found:             64.48     5.01   8.27                                      ______________________________________                                    

EXAMPLE 17 4-(4-((6-Chloro-2-quinoxalinyl)oxy)phenoxy)-2-penten-1-ol,methylcarbamate ##STR107##

To a solution of 1.78 g (5 mmol) of the pentenol obtained in Example 3above, was added 3 drops of triethylamine, 0.86 g (15 mmol) ofmethylisocyanate and 50 ml of methylene chloride. The solution wasstirred at room temperature for 8 days. The solvent was separated andthe residue was recrystallized twice from methylcyclohexane to give 1.68g (81%) of the desired carbamate product as colorless crystals. Theproduct melted at 114°-115° C. (Compound 31).

    ______________________________________                                        Elemental Analysis:                                                                            % C     % H    % N                                           ______________________________________                                        Calculated for C.sub.21 H.sub.20 ClN.sub.3 O.sub.4 :                                             60.97     4.87   10.15                                     Found:             60.69     4.81   10.43                                     ______________________________________                                    

The compounds of the present invention have been found to be suitablefor use in methods for the selective postemergent control of many annualand perennial grassy weeds in the presence of corn plants. It is to benoted that not all compounds will have the same effect on all weedplants. Some compounds will be more active in the control of one weedspecie than another.

For such uses, unmodified active ingredients of the present inventioncan be employed. However, the present invention also embraces the use ofthe active compounds in admixture with inert materials, known in the artas agricultural adjuvants and/or carriers, in solid or liquid form.Thus, for example, an active ingredient can be dispersed on afinely-divided solid and employed therein as a dust or granule. Also,the active ingredients, as liquid concentrates or solid compositionscomprising one or more of the active ingredients can be dispersed inwater, typically with aid of a wetting agent, and the resulting aqueousdispersion employed as a spray. In other procedures, the activeingredients can be employed as a constituent of organic liquidcompositions, oil-in-water and water-in-oil emulsions or waterdispersions, with or without the addition of wetting, dispersing, oremulsifying agents. Suitable adjuvants of the foregoing type are wellknown to those skilled in the art.

The herbicidally effective concentration of the active ingredients insolid or liquid compositions generally is from about 0.0003 to about 95percent by weight or more. Concentrations from about 0.05 to about 50percent by weight are often employed. In compositions to be employed asconcentrates, the active ingredient can be present in a concentrationfrom about 5 to about 98 weight percent. The active ingredientcompositions can also contain other compatible additaments, for example,phytotoxicants, plant growth regulants and other biologically activecompounds used in agriculture.

In further embodiments, the compounds of the present invention orcompositions containing the same, can be advantageously employed incombination with one or more additional pesticidal compounds. Suchadditional pesticidal compounds may be insecticides, nematocides,miticides, arthropodicides, herbicides, fungicides or bactericides thatare compatible with the compounds of the present invention in the mediumselected for application and not antagonistic to the activity of thepresent compounds. Accordingly, in such embodiments, the pesticidalcompound is employed as a supplemental toxicant for the same or for adifferent pesticidal use or as an additament. The compounds incombination can generally be present in a ratio of from 1 to 100 partsof the compound of the present invention with from 100 to 1 part of theadditional compound(s).

The active ingredients of the present invention have been found topossess desirable postemergent activity against grassy weeds such asfoxtail, barnyard grass, wild oats, Johnson grass and crabgrass whileshowing high selectivity to corn plants. These compounds are alsouniquely effective in controlling perennial grassy weeds such as Johnsongrass, quackgrass, and bermuda grass.

The exact amount of the active material to be applied is dependent notonly on the specific active ingredient being applied, but also on theparticular action desired, the weed plant species to be controlled andthe stage of growth thereof as well as the part of the plant to becontacted with the toxic active ingredient. Thus, all of the activeingredients of the present invention and compositions containing thesame may not be equally effective at similar concentrations or againstthe same weed plant species.

In the present postemergent operations, a dosage of about 0.01 to about20 lbs/acre (0.056-22.4 kg/hectare) is generally applicable, althoughnot all compounds are equally effective and some weeds are moredifficult to control. Thus, a dosage rate in the range of about 0.05 toabout 1.0 lb/acre (0.01-1.12 kg/hectare) is preferred in postemergentcontrol of annual grassy weeds, while about 0.05 to about 5 lbs/acre(0.056-5.6 kg/hectare) is a preferred dosage range for the postemergentcontrol of perennial grassy weeds. In applications to corn plants a weedcontrolling but less than corn plant damaging amount of from about 0.005to about 1.0 lb/acre (0.0056 to 1.12 kgs/hectare) is generally employed.

The following examples illustrate the effects of the compounds of thisinvention.

EXAMPLE 18

Representative compositions of the present invention were evaluated todetermine their effectiveness in postemergent operations.

Aqueous dispersions were prepared by admixing predetermined amounts ofone of the hereinafter set forth compounds, dissolved in a predeterminedamount of an inert solvent with a predetermined quantity of water and apredetermined amount of a surfactant to give aqueous dispersions of oneof compounds 1-26 as the sole toxicant.

Seeds of various plant species were planted in beds of good agriculturalsoil and grown in a greenhouse. After the plants had emerged and hadgrown to a height of from 2-8 inches (depending on the plant species),separate beds of the plants were sprayed to runoff with one of theabove-prepared compositions at a predetermined treating rate (in partsof the active compound per million parts of the ultimate composition(PPM)). Other beds of the plants were sprayed with a water-surfactantmixture, containing no active compound, to serve as controls. Aftertreatment, the beds were maintained for two weeks under greenhouseconditions conducive for good plant growth. At the end of this period,the beds were examined to determine the amount of kill and control. Thespecific plant species, test compounds and the percent postemergentcontrol are set forth below in Table 11.

                                      TABLE 11                                    __________________________________________________________________________    Compound                                                                            Treatment                                                                            Percent Kill and Control of the Following Plant Species          No. Tested                                                                          Rate in PPM                                                                          Corn                                                                             Crabgrass                                                                           Johnson Grass                                                                         Giant Foxtail                                                                        Green Foxtail                            __________________________________________________________________________    1     1000   0  NT    90      85     90                                             500    0  NT    75      85     80                                       2     500    0  100   NT      100    100                                            250    0  100   NT      100    100                                      3     1000   0  NT    40      90     85                                             500    0  NT    10      90     80                                       4     125    60 NT    100     100    100                                            62     20 NT    90      100    80                                       5     125    20 NT    100     100    100                                            62     0  NT    100     100    100                                      6     125    20 NT    100     100    100                                            62     0  NT    90      90     100                                      7     250    0  NT    100     100    100                                            125    0  NT    100     100    100                                      8     500    0  80    NT      98     98                                             250    0  80    NT      100    98                                       9     500    0  100   NT      100    100                                            250    0  100   NT      100    100                                      10    500    0  98    NT      100    100                                            250    0  70    NT      98     100                                      11    500    0  95    NT      100    98                                             250    0  90    NT      100    98                                       12    500    0  100   NT      100    100                                            250    0  100   NT      100    100                                      13    125    0  NT    NT      95     NT                                             62     0  NT    NT      90     NT                                       14    500    10 NT    100     100    100                                            250    0  NT    100     100    100                                      15    500    20 NT    100     100    100                                            250    0  NT    100     100    100                                      16    500    0  NT    NT      90     NT                                             250    0  NT    NT      95     NT                                       17    250    10 NT    100     100    100                                            125    0  NT    100     60     100                                      18    62     10 NT    100     100    100                                            31     0  NT    80      90     20                                       19    125    20 NT    100     100    100                                            62     0  NT    100     100    100                                      20    500    10 NT    100     100    100                                            250    0  NT    100     100    100                                      21    250    20 NT    100     100    100                                            125    0  NT    100     90     50                                       22    500    20 NT    100     100    100                                            250    0  NT    100     100    100                                      23    250    20 NT    100     100    100                                            125    0  NT    100     90     95                                       24    250    0  NT    NT      94     NT                                             125    0  NT    NT      92     NT                                       25    250    5  NT    NT      90     NT                                             125    5  NT    NT      90     NT                                       26    250    5  NT    NT      98     NT                                             125    0  NT    NT      98     NT                                       __________________________________________________________________________

What is claimed is:
 1. A compound or an optical isomer thereofcorresponding to the formula ##STR108## wherein Ar represents ##STR109##Y and Y¹ each independently represent --H or --F; R represents methyl orethyl;T represents ##STR110## and the cis (Z) or trans (E) stereoisomersthereof or ##STR111## a represents the integer 0, 1 or 2; b representsthe integer 1 or 2; P represents --Br, --Cl, --I or --CF₃ ; R¹represents --SO₂ R², ##STR112## R² represents C₁ -C₄ alkyl, C₂ -C₄alkenyl or --NR⁴ R⁵ ; R³ represents C₂ -C₄ alkenyl, C₁ -C₄ alkyl, --NR⁴R⁵ or ##STR113## wherein R⁴ and R⁵ each independently represent --H orC₁ -C₄ alkyl;D represents C₁ -C₄ -alkyl, --Br, --Cl, --NO₂, --CF₃,--OCF₃, ##STR114## wherein R⁶ represents C₁ -C₄ alkyl and m representsan integer of from 0-3, inclusive.
 2. A compound as defined in claim 1which is in the R enantiomeric isomer form.
 3. A compound as defined inclaim 1 which is in the E stereoisomer form.
 4. A compound as defined inclaim 1 wherein P is --I.
 5. A composition which comprises anagriculturally acceptable inert adjuvant in intimate admixture with aherbicidally effective amount of a compound, as the active material,which corresponds to the formula ##STR115## wherein Ar represents##STR116## Y and Y¹ each independently represent --H or --F; Rrepresents methyl or ethyl;T represents ##STR117## and the cis (Z) ortrans (E) stereoisomers thereof or a represents the integer 0, 1 or 2; brepresents the integer 1 or 2; P represents --Br, --Cl, --I or --CF₃ ;R¹ represents --SO₂ R², ##STR118## R² represents C₁ -C₄ alkyl, C₂ -C₄alkenyl or --NR⁴ R⁵ ; R³ represents C₂ -C₄ alkenyl, C₁ -C₄ alkyl, --NR⁴R⁵ or ##STR119## wherein R⁴ and R⁵ each independently represents --H orC₁ -C₄ alkyl; D represents C₁ -C₄ -alkyl, --Br, --Cl, --NO₂, --CF₃,--OCF₃, ##STR120## wherein R⁶ represents C₁ -C₄ alkyl and m representsan integer of from 0-3, inclusive.
 6. A composition as defined in claim5 wherein the compound is in the R enantiomeric isomer form.
 7. Acomposition as defined in claim 5 wherein the compound is in the Estereoisomer form.
 8. A composition as defined in claim 5 wherein P is--I.
 9. A method for the postemergent kill and control of grassy weedswhich comprises applying to said weeds a herbicidally effective amountof a composition comprising an agriculturally acceptable inert adjuvantin intimate admixture with, as the active material, a compoundcorresponding to the formula ##STR121## wherein Ar represents ##STR122##Y and Y¹ each independently represent --H or --F; R represents methyl orethyl;T represents ##STR123## and the cis (Z) or trans (E) stereoisomersthereof or ##STR124## a represents the integer 0, 1 or 2; b representsthe integer 1 or 2; P represents --Br, --Cl, --I or --CF₃ ; R¹represents --SO₂ R², ##STR125## R² represents C₁ -C₄ alkyl, C₂ -C₄alkenyl or --NR⁴ R⁵ ; R³ represents C₂ -C₄ alkenyl, C₁ -C₄ alkyl, --NR⁴R⁵ or ##STR126## wherein R⁴ and R⁵ each independently represent --H orC₁ -C₄ alkyl; D represents C₁ -C₄ -alkyl, --Br, --Cl, --NO₂, --CF₃,--OCF₃, ##STR127## wherein R⁶ represents C₁ -C₄ alkyl and m representsan integer of from 0-3, inclusive.
 10. A method as defined in claim 9wherein the grassy weeds are selectively killed and controlled in thepresence of corn plants.
 11. A method as defined in claim 10 which is inthe R enantiomeric isomer form.
 12. A method as defined in claim 10which is in the E stereoisomer form.
 13. A method as defined in claim 10wherein P is --I.